Journal of Food Engineering 81 (2007) 236242 www.elsevier.

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Study of solidliquid extraction kinetics of total polyphenols from grape seeds

-Kojic *, Mirela Planinic , Srec ko Tomas, Mate Bilic , Darko Velic Ana Bucic
a 18, Department of Process Engineering, Faculty of Food Technology, Josip Juraj Strossmayer, University of Osijek, F. Kuhac P.O. Box 709, HR-31001 Osijek, Croatia Received 12 April 2006; received in revised form 5 September 2006; accepted 29 October 2006 Available online 13 December 2006

Abstract Grape seeds are a waste by-product obtained after wine or juice making and present a good source of functional compounds, such as polyphenols. Extraction is a very important step for later use of phenolic components. The eect of dierent temperatures and solid liquid ratios on the solidliquid extraction yield of total polyphenols and the eect of four classes of particle size on the extraction kinetics of total polyphenols with 50% of aqueous ethanol were studied. Temperature, solidliquid ratio and milling degree had positive inuence on extraction rate and extent of extraction. The 1.476.68% of total polyphenols per dry matter of grape seeds was extracted during 200 min. Extraction kinetics was estimated using non-experimental two-parameter equation modied Pelegs model. Results showed a good prediction of Pelegs model for extraction kinetics in all experiments (q > 0.994), which gave the possibility for estimation of initial rate and extent of solidliquid extraction. 2006 Elsevier Ltd. All rights reserved.
Keywords: Grape seeds; Total polyphenols; Solidliquid extraction; 50% Aqueous ethanol; Temperatures; Solidliquid ratio; Particle size; Pelegs model

1. Introduction The interest in the investigation of active components, especially polyphenols, from natural sources (fruits, vegetables, cereals, herbs) has greatly increased in recent years. The reason for that is restricted use of synthetic antioxidants such as butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) in foods because of their possible undesirable eects on human health (Jayaprakasha, Selvi, & Sakariah, 2003). During winemaking or juice making from grape high quantities of waste by-products (grape pulp, seeds, skin) remain, which are used only as a feed for animals due to their high bre content (Palma, Pin eiro, & Barroso, 2001). However, these by-products are still a good and cheap source of high-quality polyphenolic compounds
*

Corresponding author. Tel.: +385 31 224 334; fax: +385 31 207 115. -Kojic ). E-mail address: ana.bucic@ptfos.hr (A. Bucic

which can be used in dierent therapeutic procedures with the purpose of free radical neutralisation in biological systems (Heim, Tagliaferro, & Bobilya, 2002; Yilmaz & Toledo, 2004). Grape seeds contain 58% polyphenols according to Shi, Yu, Pohorly, and Kakuda (2003a). Extraction is a very important stage in isolation, identication and use of phenolic compounds and there is no single and standard extraction method. Solidliquid extraction of zphenolic compounds with dierent solvents (Baydar, O dic ek, & Golc Wondra, kan, & Sag , 2004; Lapornik, Pros , Kovac , Alonso, & Revilla, 1998) and in some 2005; Pekic cases extraction with supercritical uid (Palma & Taylor, 1999) are the most common by used techniques for isolation of these compounds. To describe extraction mechanism in the literature, Ficks second law of diusion is usually used (Cacace & Mazza, 2003; Stangler Herodez , kerget, & Knez, 2003). Many authors investiHadolin, S gated solidliquid extraction of natural antioxidants and their properties from grape seed (Jayaprakasha et al.,

0260-8774/$ - see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.jfoodeng.2006.10.027

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2003; Shi et al., 2003a; Yilmaz & Toledo, 2004) and from other plant materials (Bandoniene , Pukalskas, Venskuto kerget et al., nis, & Gruzdiene , 2000; Moure et al., 2001; S 2005) as well as methods for their identication (Guendez, Kallithraka, Makris, & Kefalas, 2005; Tsao & Deng, 2004). However, literature data about optimisation (Pinelo, Del Fabbro, Manzocco, Nun ez, & Nicoli, 2005; Shi et al., 2003b), modelling and simulation of solidliquid extraction process are scarce. Therefore, there is a need for mathematical modelling, as a useful engineering tool, which considerably facilitates optimisation, simulation, design and control of processes and contributes to utilization of energy, time and solvent. On the other hand, dierent mathematical models are often used for the description of sorption processes (dehydration/rehydration) of food materials. One of them is a two-parameter, non-exponential Pelegs model (Abu-Ghannam & McKenna, 1997; Hung, Liu, Black, & Trewhella, 1993; Maskan, 2002; Moreira Azoubel & pez-Malo, Argaiz, & Welti, Xidieh Murr, 2004; Palou, Lo 1994; Park, Bin, Reis Brod, & Brandini Park, 2002; Peleg, , Velic , Tomas, Bilic , & Bucic , 2005; Ru z 1988; Planinic az, Martnez-Monzo D , Fito, & Chiralt, 2003; Sacchetti, Gianotti, & Dalla Rosa, 2001; Sopade & Obekpa, 1990; Turhan, Sayar, & Gunasekaran, 2002). Because of a similarity between extraction and sorption kinetics, our goal was to examine the applicability of Pelegs equation for modelling the extraction of total polyphenols from grape seeds. The aim of this work was to also determine the best temperature, particle size and solid liquid ratio for solidliquid extraction of total polyphenols under experimental conditions. Quantication of individual polyphenols in extract was not in the issue of this paper. 2. Materials and methods 2.1. Sample preparation White grapes were produced in a private plantation located in Eastern Slavonia. Grape seeds were residual after wine making which were manually separated from the pomace and sun dried (dry matter content 91%). Dried seeds were stored at room temperature and milled in coee grinders before extraction. Determination of dry matter content: Dry matter content of grape seeds was determined by drying of milled grape seeds (5 g) at 105 C to constant mass. Analyses were done in duplicate and the average dry matter content (wdb) was expressed in percents (%) and calculated by the following formula: m2 100 1 wdb m1 where m1 is a mass of grape seed before drying (g) and m2 is the mass of grape seed after drying (g). Sample preparation for the investigation of extraction yield: Grape seeds were milled in a coee grinder (SMK

101, Gorenje) for 2 min with 15 s intervals to avoid heating of the samples. Sample preparation for the study of extraction kinetics: Grape seeds were milled in a coee grinder with the possibility of particle size regulations (MKM 7000, Bosch) and separated by sieving into four particle classes: (>0.63 mm), (0.630.4 mm), (0.40.16 mm) and (0.16 0.125 mm). After grinding, the samples were immediately vacuum packed and stored at +4 C before extraction. 2.2. Extraction process Extracts from milled grape seed were prepared by using 50% aqueous ethanol as a solvent. Each extraction was performed in triplicate. Determination of extraction yield: In the test tubes, 0.5 g of non-classed sample was mixed with 5 ml, 10 ml, 15 ml or 20 ml of solvent to obtain dierent solidliquid ratios (L/S) of 10 ml/g, 20 ml/g, 30 ml/g and 40 ml/g, respectively. Test tubes were incubated in the water bath at dierent temperatures (25 C, 40 C, 50 C, 60 C, 70 C, 80 C) for 120 min with 20-s shaking of each test tube at 15 min intervals by Vortex (Vibromix 10, Tehtnica). Monitoring of extraction kinetics: The highest extraction yield was obtained at a solidliquid ratio of 40 ml/g as shown in Fig. 1. So, the solidliquid ratio of 40 ml/g was used for the purpose of kinetic study at dierent extraction temperatures (25 C, 50 C, 80 C). Extraction kinetic was observed on three classes of particles: (>0.63 mm), (0.63 0.4 mm), (0.40.16 mm) at 25 C, 50 C and 80 C and on one more class (0.160.125 mm) at 80 C. The extraction kinetics was observed during 200 min with periodical shaking as previously described. In both ways, the extracts were separated from rough particles after extraction by decantation and were centrifuged for 5 min on 15 000g (Multifuga 3 L-R Heraeus, Kendro Laboratory Products). The supernatants were measured and pooled to 25 ml by using 50% aqueous ethanol. The extract prepared in this way was used for further spectrophotometric determination of total polyphenols.

Fig. 1. The inuence of extraction temperature and solidliquid ratio (L/S) on extraction yield of total polyphenol concentrations from nonclassed milled grape seeds.

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2.3. Determination of total polyphenols The concentration of total polyphenols in the extracts was determined by spectrophotometric FolinCiocalteau method according to Lapornik et al. (2005) with some modications. 0.2 ml of the extract was mixed with 1.8 ml of distilled water and 10 ml of 10-fold diluted FolinCiocalteau reagent. After 30 s to 8 min, 8 ml of 7.5% of sodium carbonate solution was added. All test tubes with the mixture were shaken for 10 s on the Vortex and put on to incubation in a water bath at 45 C. Absorbance was measured after 15 min at 765 nm (UV/VIS 554, PerkinElmer Spectrophotometer) against blank sample. Blank sample was prepared with water instead of the extract. Determination of total phenolic compounds was carried out in a duplicate and calculated from the calibration curve obtained with gallic acid, which was used as a standard and results were expressed as mg GAE/ml. The nal results were calculated by the following formula taken from Waterman and Mole (1994), which was adapted to experimental conditions and expressed in gallic acid equivalent per a dry basis of grape seeds (mg GAE/ gdb)   V1 1 100 C c V 2 V 3 2 ms wdb V2 where C is concentration of total polyphenols (mg GAE/ gdb), c the concentration of total polyphenols (mg GAE/ ml), V1 the volume of gained extract after solidliquid extraction (ml), V2 the volume of extract taken from V1 for the preparation of diluted extract (ml), V3 the volume of extraction solvent used for the dilution of extract to a total volume of 25 ml (ml), ms the mass of grape seed used in extraction (g) and wdb the content of dry matter (%). 2.4. Kinetic of solidliquid-extraction As mentioned in the introduction and conrmed by this experimental work, the extraction curves (concentration of total polyphenols vs. time) have similar shape with the sorption curves (moisture content vs. time), so, all these curves could be described by the same model proposed by Peleg (1988) which in case of extraction would assume the form: t C t C 0 3 K1 K2 t where C(t) is the concentration of total polyphenols at time t (mg GAE/gdb), t the extraction time (min), C0 the initial concentration of total polyphenols at time t = 0 (mg GAE/ gdb), K1 is Pelegs rate constant (min gdb/mg GAE) and K2 is Pelegs capacity constant (gdb/mg GAE). Since C0 in all experimental runs was zero, Eq. (3) was used in the nal form t C t 4 K1 K2 t

The Peleg rate constant K1 relates to extraction rate (B0) at the very beginning (t = t0) B0 1 mg GAE=gdb min K1 5

The Peleg capacity constant K2 relates to maximum of extraction yield, i.e. equilibrium concentration of extracted total polyphenols (Ce). When t ? 1, Eq. (6) gives the relations between equilibrium concentration and K2 constant C jt!1 C e 1 mg GAE=gdb K2 6

2.5. Statistical methods Statistica 6.0 (Stat Soft Inc., USA) was used for data analysing. The randomized complete block designed (RCBD) was served as experimental scheme for two factorial analyses. The analysis of variance (ANOVA) and F-test were used to assess the factor inuence on extraction and their possible interaction under conditions in this study. The parameters of modied Pelegs model (constants K1 and K2) were determined from experimental data using non-linear regression (Quasi-Newton method). The concordance between experimental data and calculated value was established by the correlation coecient (q) and the root mean squared deviation (RMSD) as follows: s n 1X 2 7 RMSD experimental calculated n i1 3. Results and discussion Dry matter content in all experimental runs was determined and results were expressed on dry basis, which generally provides more accurate and reliable data comparison. Solidliquid extraction was carried out by 50% aqueous ethanol for 200 min, which gave concentration of total polyphenols in the range from 14.72 mg GAE/gdb to 66.81 mg GAE/gdb and represented 1.47 6.68% per dry matter of seeds that was compatible with the results reported by Shi et al. (2003b). They were extracted 15.15339.246 mg GAE/gseed of total polyphenols by using 50% aqueous ethanol. Other authors also obtained similar results using dierent solvents. Jayaprakasha et al. (2003) gained 38% (w/w) and 46% (w/w) of total polyphenols (catehin equivalents) per crude extract by using acetonewateracetic acid and methanolwateracetic acid, which when recalculated on grape seed were 2.13% and 2.57%, respectively; Baydar et al. (2004) extracted 9.65% and 10.86% of total polyphenols on seed base by using acetonewateracetic and ethyl methanolwater, respectively, Guendez et al. (2005) obtained the average of 3.8 mg GAE/gseed extracted by ethyl acetate.

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C (mg GAE/gdb)

3.0.1. Inuence of solidliquid ratios and temperatures on the extraction yield of total polyphenols The estimation of extraction yield was based on the concentrations of extracted total polyphenols from nonclassed milled grape seed. The concentrations were calculated according to Eq. (2) and the results are shown in Fig. 1. Statistical data processing was carried out by 6 4 RCBD and the results are shown in Table 1. On the basis of F-value magnitudes, no statistical by signicant dierence (P = 0.05) between six repetitions of each extraction was found, but high by signicant F-value of combinations occurred (six temperatures and four solidliquid ratios). These results implied signicant dierence of the polyphenols concentration depending on temperature and solidliquid ratio. Further ANOVA analysis showed that temperature and solidliquid ratio had statistical by significant inuence on extraction yield of total polyphenols. Besides, interaction between extraction temperature and solidliquid ratio was observed, which indicated that extraction temperature had a dierent inuence on extraction yield at dierent solidliquid ratios. The L/S = 40 ml/g gave mostly the best extraction yield at all tested temperatures, so this solidliquid ratio was used for the examination of extraction kinetics. The highest polyphenols yield (30.243 mg GAE/gdb) was obtained at 80 C and L/S = 40 ml/g (Fig. 1). 3.0.2. Solidliquid extraction kinetics of total polyphenols The inuence of particles size on solidliquid extraction kinetics at 80 C and solidliquid ratio of 40 ml/g can be seen in Fig. 2. The results and extraction curves indicated the exponential growth of extraction rate in the time for all examined particle classes. The total concentration of extracted polyphenols was the highest during extraction from the smallest particle class (0.160.125 mm) in the amount of 66.810 mg GAE/gdb, and the lowest in the case of the biggest particle size (>0.63 mm) in the amount of 23.907 mg GAE/gdb. However, coecient of variation of repetition was increased from the highest to the lowest par-

80 60 40 20
(> 0.63) mm (0.63 - 0.4) mm (0.16 - 0.125) mm

0 0 50

(0.4 - 0.16) mm

100

150

200

t (min)
Fig. 2. The inuence of particle size on total polyphenols extraction at 80 C and L/S = 40 ml/g for dierent particle classes (symbols experimental data; lines approximation curves).

ticles (2.33%, 2.49%, 6.57% and 12.61%, respectively), which implied the highest data dispersions for (0.16 0.125 mm) particle class as a consequence of the possible agglomeration of smaller particles, so this fraction was omitted in the further experimental work (extraction at 25 C and 50 C). A similar pattern of extraction curves (curves are not shown) was obtained at temperatures 25 C and 50 C for three particle classes but with dierent extraction extent (Table 2). From these results, great temperature inuence on extraction kinetics of total polyphenols from grape seeds can be observed. In addition to that, high initial rate of polyphenols extraction (rst 40 min) can be seen from extraction curves, followed by slower extraction rate, and asymptotically approaching the equilibrium concentration. The Fig. 3ac shows the eect of extraction temperatures (25 C, 50 C, 80 C) on the extraction kinetics of total polyphenols for each particle class (>0.63, 0.630.4 and 0.40.16 mm). In the case of particle size (>0.63 mm) the highest concentration of total polyphenols was obtained at 80 C, and the lowest concentration at 25 C (Fig. 3a, Table 2). The same relation was obtained for particle class (0.630.4 mm) (Fig. 3b, Table 2). The extraction rate and extraction extent obtained from particle class (0.4 0.16 mm) were a little higher at 50 C than 80 C (Fig. 3c, Table 2). This can be explained by possible agglomeration

Table 1 Results of statistical analysis (6 4 RCBD) Source of variation Total Repetitions Combinations Error Eects Temperature of extraction (#) Solidliquid ratio (L/S) Interaction of eects (# L/S) 5 3 15 759.59 542.16 57.33 151.92 180.72 3.82 261.20b 310.72b 6.57b 2.29 2.69 1.85 df 143 5 23 115 SS 1427.76 1.80 1359.08 66.885 s2 0.36 59.09 0.58 Fexp 0.62a 101.60b Fcrit P = 0.05 2.29 1.62

df degrees of freedom; SS sum of squares; s2 variance, Fexp, Fcrit experimental and critical Fisher coecients. a Statistically insignicant. b Statistically signicant.

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Table 2 Values of extraction extent, Pelegs constants (K1 and K2) for solidliquid extraction with correlation coecient (q) and the root mean squared deviation (RMSD) at dierent particle size and extraction temperature Particle size (mm) (>0.63) Temperature (C) 25 50 80 25 50 80 25 50 80 80 Extraction extent (mg GAE/gdb) 14.7193 20.2015 23.9074 22.0303 23.7196 26.5784 52.6011 56.4722 54.3745 66.8097 K1 (min gdb/mg GAE) 1.1541 0.6571 0.7101 0.4256 0.3037 0.3056 0.0814 0.0645 0.0869 0.0400 K2 (gdb/mg GAE) 0.0651 0.0481 0.0393 0.0448 0.0416 0.0375 0.0193 0.0175 0.0184 0.0156 q 0.9944 0.9969 0.9983 0.9957 0.9981 0.9967 0.9972 0.9985 0.9985 0.9945 RMSD 0.4179 0.4258 0.3847 0.5297 0.3787 0.5564 0.9945 0.7990 0.7664 1.7490

(0.630.4)

(0.40.16)

(0.160.125)

80

25C

50C

80C

60 40 20 0 0 50

a
80

100 t (min)
25C

150

200

50C

80C

60 40 20 0 0 50

b
80

100 t (min)
25C

150

200

50C

80C

60 40 20 0 0 50

100 t (min)

150

200

Fig. 3. The temperature inuence on solidliquid extraction of total polyphenols for dierent particle classes of grape seeds: (a) (>0.63 mm), (b) (0.630.4 mm) and (c) (0.40.16 mm) (symbols experimental data; lines approximation curves).

of smaller particles, as mentioned earlier, which can cause experimental errors. Moreover, extraction of proteins is better at lower temperatures by alcohol solution with high water ratio (Shi et al., 2003b) and it is known that proteins give positive reaction with FolinCiocalteau reagent, which can cause interference in spectrophotometric determination of total polyphenols. This course of extractions (Figs. 2 and 3ac) shows similarity with course of sorption processes, which can be well et al., described by Pelegs model (Peleg, 1988; Planinic 2005). The modied Pelegs model (Eq. (4)) adapted to experimental condition was used for experimental data approximation. The experimental extraction extent, calculated parameters of modied Pelegs model (constants K1 and K2), correlation coecient (q) and RMSD are shown in Table 2. The correlation coecients were high in all experiments (q > 0.994) which implied good concordance between experimental and calculated data. The RMSD had relatively low values for (>0.63 mm) and (0.63 0.4 mm) particle classes, while with further decrease of particle size this RMSD value was a little higher. The values of extraction rate constant (K1) and constant of extraction extent (K2) showed a tendency of decrease with the increase of extraction temperature and the decrease of particles size. The dierence in extraction extent was analysed by using the scheme of 32 RCBD. The results indicated no signicant dierence (P = 0.01) in total polyphenol concentrations after 200 min (extraction extent) between six repetitions of each extraction, but high signicant F-value of combinations (three temperatures and three particle classes). Interaction of factors (temperature and particle size) was also observed. So, this observation implied a signicant dierence in extraction extent in view of extraction temperatures and particles size. The initial extraction rate (Eq. (5)) and maximum of extraction extent in experimental conditions (Eq. (6)) were calculated from constants K1 and K2.. Fig. 4 shows the inuence of particle size on initial extraction rate (1/K1) at 80 C and L/S = 40 ml/g (the best experimental conditions, as mentioned above). The exponential decrease of initial extraction rate with an increase of particle size

C (mg GAE/gdb)

C (mg GAE/gdb)

C (mg GAE/gdb)

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1/K1 (mg GAE/mingdb)

30

20

smaller particles and that was conrmed by value of energy activation which was in the amounts of 8.01 kJ/ mol, 2.82 kJ/mol and 0.71 kJ/mol for particle size: (>0.63 mm), (0.630.4 mm) and (0.40.16 mm), respectively.
R2 = 0.9967

10

4. Conclusion
0.8

0 0.0

0.2

0.4 0.6 particle size (mm)

Fig. 4. Eect of average particle size of each class on the initial extraction rate, 1/K1 at 80 C and L/S = 40 ml/g (symbols experimental data; lines approximation curves).

implied strong dependence of initial extraction rate on particle size as can be seen in Figs. 2 and 3, too. The temperature inuence on initial extraction rate (1/K1) for dierent particles size was assessed by linearized Arrhenius equation, which gave relationship between 1/K1 and extraction temperatures as follows ln 1 Ea ln K 0 K1 RT 8

where K0 is constant (mg GAE/gdb min), Ea the activation energy (kJ/mol), R the universal gas constant (8.314 kJ/ mol K), and T the absolute temperature (K). The calculated activation energies (Eq. (8)) for average particles size of each class (>0.63, 0.630.4 and 0.4 0.16 mm) were 7.70 kJ/mol, 5.27 kJ/mol and 1.10 kJ/mol, respectively (results are not shown). These results implied that initial extraction rate (1/K1) tends to be more temperature sensitive for bigger rather than for smaller particles. In other words, raise of extraction temperature will aect the initial extraction rate of bigger particles more than that of smaller particles. In the same manner, extraction extent (1/K2) in experimental condition was decreased with increase of particle size and showed exponential trend, as presented in Fig. 5. The inuence of extraction temperature on extraction extent was stronger on the bigger particles than the

At experimental condition in this study, the yield and kinetic of solidliquid extraction were inuenced by the temperature, solidliquid ratio and particle size. The extracted total polyphenols were in the range from 14.72 mg GAE/gdb to 66.81 mg GAE/gdb under experimental conditions. The Peleg equation showed to be suitable to model the solidliquid extraction kinetics of total polyphenols from grape seeds at tested conditions, which was proved by high correlation coecient in all experiments (q > 0.994) and relatively low RMSD (0.37871.7490). The 8090% of total polyphenols reached within 200 min was extracted in the rst 40 min of extraction. The temperature and particle size, as well as their interaction had high inuence on solidliquid extraction kinetics. The values of initial extraction rate, 1/K1, and extraction extent, 1/K2, increased with the decrease of the particles size and showed exponential trend. The extraction temperature had bigger inuence on initial extraction rate and extraction extent for bigger than for smaller particles, which were proved by the highest value of energy activation. The results of this work could contribute in the simulation and optimization of extraction kinetics for grape seed. Acknowledgement This work was nancially supported by the Ministry of Science, Education and Sports of the Republic of Croatia, Project No. 0113005. References
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80 1/K2 (mg GAE/gdb) 60 40 20 0 0.0 R2 = 0.9573

0.2

0.4 0.6 particle size (mm)

0.8

Fig. 5. Eect of average particle size of each class on the extraction extent 1/K2 at 80 C and L/S = 40 ml/g (symbols experimental data; lines approximation curves).

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